The potency of hydrothermally prepared sulfated silica (SO4/SiO2) as a heterogeneous acid catalyst for ethanol dehydration into diethyl ether.

The dehydration of ethanol into diethyl ether over a SO4/SiO2 catalyst was investigated. The SO4/SiO2 catalysts were prepared by the sulfation method using 1, 2, and 3 M of sulfuric acid (SS1, SS2, and SS3) via hydrothermal treatment. This study is focused on the synthesis of a SO4/SiO2 catalyst with high total acidity that can be subsequently utilized to convert ethanol into diethyl ether. The total acidity test revealed that the sulfation process increased the total acidity of SiO2. The SS2 catalyst (with 2 M sulfuric acid) displayed the highest total acidity of 7.77 mmol/g, whereas the SiO2 total acidity was only 0.11 mmol/g. Meanwhile, the SS3 catalyst (with 3 M sulfuric acid) has a lower total acidity of 7.09 mmol/g due to the distribution of sulfate groups on the surface having reached its optimum condition. The crystallinity and structure of the SS2 catalyst were not affected by the hydrothermal treatment or the sulfate process on silica. Furthermore, The SS2 catalyst characteristics in the presence of sulfate lead to a flaky surface in the morphology and non-uniform particle size. In addition, the surface area and pore volume of the SS2 catalyst decreased (482.56-172.26 m2/g) and (0.297-0.253 cc/g), respectively, because of the presence of sulfate on the silica surface. The SS2 catalyst's pore shape information explains the formation of non-uniform pore sizes and shapes. Finally, the activity and selectivity of SO4/SiO2 catalysts in the conversion of ethanol to diethyl ether yielded the highest ethanol conversion of 70.01% and diethyl ether product of 9.05% from the SS2 catalyst (the catalyst with the highest total acidity). Variations in temperature reaction conditions (175-225 °C) show an optimum reaction temperature to produce diethyl ether at 200 °C (11.36%).

Photocatalytic degradation of naphthol blue from Batik wastewater using functionalized TiO2-based composites.

This work provides a first-time comparative study examining the photocatalytic activity of functionalized TiO2-based composites to eliminate naphthol blue in Batik wastewater. Reduced graphene oxide (RGO) was synthesized by oxidizing solid graphite using the Hummers' method followed by sonication and reduction. N-doped TiO2 (N-TiO2) was synthesized from titanium tetrachloride (TiCl4) and urea (CH4N2O) precursors by the sol-gel method. N-TiO2 modified RGO (RGO/NT) was synthesized using a hydrothermal method from N-TiO2 and RGO. Prepared TiO2-based composites and commercial TiO2, for comparison were characterized using Fourier transform infrared spectrometer (FTIR), X-Ray diffractometer (XRD), scanning electron microscope-energy dispersive X-ray (SEM-EDX), and UV-Vis diffuse reflectance spectrometer (UV-Vis DRS). FTIR characterization indicated Ti-N bonding in N-TiO2 and RGO/NT. XRD patterns showed that commercial TiO2 had a rutile phase, while N-TiO2 and RGO/NT had an anatase phase with crystal sizes of 30.09, 16.28, and 12.02 nm, respectively. SEM results displayed the presence of small and glossy white N-TiO2 dispersed on the surface of RGO. Characterization using UV-Vis DRS showed that the band gap energy values for TiO2, N-TiO2, and RGO/NT were 3.25, 3.12, and 3.08 eV with absorption regions at the wavelengths of 382, 398, and 403 nm, respectively. The highest photocatalytic activity for RGO/NT for degrading naphthol blue was obtained at pH 5, with a photocatalyst mass of 60 mg, and an irradiation of 15 min. Photocatalytic degradation by RGO/NT on Batik wastewater under visible light showed higher effectivity than under UV light.

Hydrocracking optimization of palm oil to bio-gasoline and bio-aviation fuels using molybdenum nitride-bentonite catalyst.

In this study, molybdenum nitride-bentonite was successfully employed for the reaction of hydrocracking of palm oil to produce a bio-gasoline and bio-aviation fuel. The prepared catalyst was characterized using XRD, FT-IR, and SEM-EDX. The acidity of the catalyst was determined using the pyridine gravimetric method. The result showed that the acidity of bentonite was increased after modification using molybdenum nitride. The hydrocracking study showed that the highest conversion and product fraction of bio-gasoline and bio-aviation fuel were exhibited by molybdenum nitride-bentonite 8 mEq g-1. The catalyst was later used to optimize the hydrocracking process using RSM-CCD. The effects of the process variables such as temperature, contact time, and catalyst to feed ratio, on the response variables, such as conversion, oil, gas, and coke yield, were investigated. The analysis of variance showed that the proposed quadratic model was statistically significant with adequate precision to estimate the responses. The optimum conditions in the hydrocracking process were achieved at a temperature of 731.94 K, contact time of 0.12 h, and a catalyst to feed ratio of 0.12 w/v with a conversion of 78.33%, an oil yield of 50.32%, gas yield of 44.00% and coke yield of 5.73%. The RSM-CCD was demonstrated as a suitable method for estimating the hydrocracking process of palm oil using a MoN-bentonite catalyst due to its closeness to the optimal value of the expected yield. This study provided a potential catalyst of based on bentonite modified using molybdenum nitride for the hydrocracking of palm oil.

Antimicrobial Imperata cylindrica paper coated with anionic nanocellulose crosslinked with cationic ions.

Recently, the interest in active packaging utilization has increased with population growth, food demand and new consumer trend like food delivery services. This new system, however, requires the use of additives to extend the food product quality and safety as well as in maintaining the shelf-life. This study was to prepare the antimicrobial paper from I. cylindrica coated anionic nanocellulose crosslinked cationic to create a system with the ability to actively control microbe growth in the packaging materials. The process involved pulping of I. cylindrica using semi-chemical and soda chemical method. The antimicrobial paper was prepared by printing the pulp suspension in 60 g/m2 grammage in mold followed by the spray of anionic nanocellulose and subsequent soaking of the paper in cationic solution. The results showed the I. cylindrica paper coated anionic nanocellulose crosslinked with H+ and Al3+ cations were successfully produced. The paper produced was also observed to have antimicrobial activity against Gram-negative of E. coli and S. typhi as well as Gram-positive of S. aureus and B. subtilis bacteria. Furthermore, the best coating method was found on antimicrobial paper coated anionic nanocellulose crosslinked Al3+ as evidenced by smoother and compact surface structure.

Hydrothermal preparation of a platinum-loaded sulphated nanozirconia catalyst for the effective conversion of waste low density polyethylene into gasoline-range hydrocarbons.

A platinum-loaded sulphated nanozirconia (Pt/nano ZrO2-SO4) bifunctional metal-acid catalyst was synthesized using a hydrothermal process. The nano ZrO2-SO4 was initially prepared by dispersing the nano ZrO2 in H2SO4, followed by wet impregnation via heating in an aqueous PtCl4 solution. This material was subsequently calcined and reduced under hydrogen gas to produce the catalyst. The Pt/nano ZrO2-SO4 was found to be a highly active, selective and stable solid acid catalyst for the conversion of waste low density polyethylene (LDPE) to high value hydrocarbons. The catalytic activity and stability of this material were evaluated during the hydrocracking of waste LDPE while optimizing the reaction temperature, time and catalyst-to-feed ratio. The activity of catalyst prepared by hydrothermal was attributed to highly dispersion of Pt species interacting with the support and inhibition of the agglomeration process. The impregnation method of hydrothermal generated highly active and selective catalyst with Pt loads of 1 wt%. The hydrocracking of waste LDPE over Pt/nanoZrO2-SO4 at 250 °C for 60 min with a catalyst-to-feed proportion of 1 wt% gave the largest gasoline fraction.

Base-specific and enantioselective studies for the DNA binding of iron(II) mixed-ligand complexes containing 1,10-phenanthroline and dipyrido[3,2-a:2',3'-c]phenazine.

Base specificity and enantioselectivity for the DNA binding of [Fe(phen)2(dppz)]2+ (phen=1,10-phenanthroline and dppz=dipyrido[3,2-a:2',3'-c]phenazine) have been studied by determining the equilibrium binding constant (Kb) of the iron(II) complex to calf thymus DNA (ct-DNA), poly[(dA-dT)2], poly[(dG-dC)2] and poly[(dI-dC)2] using spectrophotometric titration and by monitoring the CD spectral profile of the iron(II) complex in the presence and absence of different types of DNA using circular dichroism (CD) spectroscopy, respectively. It has been shown that [Fe(phen)2(dppz)]2+ prefers to intercalate into the A-T and I-C sequences of poly[(dA-dT)2] and poly[(dI-dC)2] rather than into the G-C sequences of poly[(dG-dC)2] or into the base pairs of ct-DNA. In contrast to previous reports, it is a surprising observation that the enantioselectivity of the DNA binding for [Fe(phen)2(dppz)]2+ is base-dependent in nature. The Delta-enantiomer of [Fe(phen)2(dppz)]2+ is preferentially intercalated into the base pairs of poly[(dG-dC)2] or ct-DNA as indicated by its CD spectral profiles. On the other hand, the Lambda-enantiomer of [Fe(phen)2(dppz)]2+ is favorably intercalated into poly[(dA-dT)2] or poly[(dI-dC)2] as suggested by the opposite CD spectral profile. This preferential binding of Lambda-[Fe(phen)2(dppz)]2+)for the A-T sequence may be attributed to the fact that the binding site for the A-T sequence is relatively facile and thus the steric effect caused by the ancillary (non-intercalated) phen ligands is alleviated. The degree of enantioselectivity represented by inversion constants (Kinv) decreases as the salt concentration in the solution increases, indicating that electrostatic interaction is also operating in the ct-DNA-binding events of the iron (II) complex.

Salt-dependent binding of iron(II) mixed-ligand complexes containing 1,10-phenanthroline and dipyrido[3,2-a:2',3'-c]phenazine to calf thymus DNA.

The salt-dependent binding of racemic iron(II) mixed-ligand complex containing 1,10-phenanthroline (phen) and dipyrido[3,2-a:2',3'-c]phenazine (dppz), [Fe(phen)2(dppz)]2+ to calf thymus DNA (ct-DNA) has been characterized by UV-VIS spectrophotometric titration. The equilibrium binding constant (Kb) of the iron(II) complex to ct-DNA decreases with the salt concentration in the solution. The slope, SK=(deltalog Kb/deltalog [Na2+]) has been found to be 0.49, suggesting that, in addition to intercalation, considerable electrostatic interaction is also involved in the ct-DNA binding of [Fe(phen)2(dppz)]2+. The calculation of non-electrostatic binding constant (Kt(o)) based on polyelectrolyte theory has revealed that the non-electrostatic contribution to the total binding constant (Kb) increases significantly with the increase in [Na+] and reaches 36% at 0.1 M NaCl. On the other hand, the contribution of the non-electrostatic binding free energy (DeltaGt(o)) to the total binding free energy change (DeltaGo) is considerably large, i.e. 87% at [Na+]=0.1 M, suggesting that the stabilization of the DNA binding is mostly due to the contribution of non-electrostatic process. Moreover, the effect of specific ligand substitutions on DeltaGo has been rigorously evaluated using the quantity DeltaDeltaGt(o), i.e. the difference in DeltaGt(o) relative to that of the parent iron(II) complex, [Fe(phen)3]2+, indicating that each substitution of phen by dip and dppz contributes 7.5 and 17.5 kJ mol(-1), respectively to more favorable ct-DNA binding.

DNA binding of iron(II) complexes with 1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline: salt effect, ligand substituent effect, base pair specificity and binding strength.

The DNA binding of iron(II) mixed-ligand complexes containing 1,10-phenanthroline(phen) and 4,7-diphenyl-1,10-phenanthroline(dip), [Fe(phen)(3)](2+), [Fe(phen)(2)(dip)](2+) and [Fe(phen)(dip)(2)](2+) has been characterized by spectrophotometric titration and melting temperature measurements. The salt concentration dependence of the binding constant has allowed us to dissect the DNA-binding constant and free energy change of each iron(II) complex into the nonelectrostatic and polyelectrolyte contributions. A comparison of the nonelectrostatic components in the binding free energy changes among iron(II) complexes has made it possible to rigorously evaluate the contribution of the ligand substituents to the DNA-binding event. The peripheral substitution of phen by two phenyl groups increases the nonelectrostatic binding constant of the iron(II) complex more than 20 times, which is equivalent to approximately 7.5 kJ mol(-1) of more favorable contribution to the DNA binding. In general, the iron(II) complexes studied have higher affinity towards the more facile A-T sequence than the G-C sequence. This preferential binding may be attributed to the steric effect induced by the ancillary part of the ligands in the course of DNA binding. The binding of disubstituted iron(II) complex to DNA is quite strong as reflected in the modest increase in the denaturation temperature (T(m)) of double helical DNA upon the interaction with the iron(II) complex.